{sup 33}S hyperfine interactions in H{sub 2}S and SO{sub 2} and revision of the sulfur nuclear magnetic shielding scale

Journal Article · Sat Dec 28 04:00:00 EST 2013 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4849177· OSTI ID:22253233

Helgaker, Trygve ^[1]; Gauss, Jürgen ^[2]; Cazzoli, Gabriele; Puzzarini, Cristina ^[3]

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1. Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Oslo, N-0315 Oslo (Norway)
2. Institut für Physikalische Chemie, Universität Mainz, D-55099 Mainz (Germany)
3. Dipartimento di Chimica “Giacomo Ciamician,” Università di Bologna, Via Selmi 2, I-40126 Bologna (Italy)

Using the Lamb-dip technique, the hyperfine structure in the rotational spectra of H{sub 2}{sup 33}S and {sup 33}SO{sub 2} has been resolved and the corresponding parameters—that is, the sulfur quadrupole-coupling and spin–rotation tensors—were determined. The experimental parameters are in good agreement with results from high-level coupled-cluster calculations, provided that up to quadruple excitations are considered in the cluster operator, sufficiently large basis sets are used, and vibrational corrections are accounted for. The {sup 33}S spin-rotation tensor for H{sub 2}S has been used to establish a new sulfur nuclear magnetic shielding scale, combining the paramagnetic part of the shielding as obtained from the spin–rotation tensor with a calculated value for the diamagnetic part as well as computed vibrational and temperature corrections. The value of 716(5) ppm obtained in this way for the sulfur shielding of H{sub 2}S is in good agreement with results from high-accuracy quantum-chemical calculations but leads to a shielding scale that is about 28 ppm lower than the one suggested previously in the literature, based on the {sup 33}S spin-rotation constant of OCS.

• OSTI ID: 22253233
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 24 Vol. 139; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ACCURACY
HYDROGEN
HYDROGEN SULFIDES
HYPERFINE STRUCTURE
INTERACTIONS
MAGNETIC SHIELDING
PARAMAGNETISM
SPECTRA
SPIN
SULFUR
SULFUR 33
SULFUR DIOXIDE
TENSORS